GB2024217A

GB2024217A - 1,3,5 - triazacyclogheptane - 2,4 - dione derivatives

Info

Publication number: GB2024217A
Application number: GB7921539A
Authority: GB
Original assignee: Chimosa Chimica Organica SpA
Current assignee: Ciba Geigy SpA
Priority date: 1978-06-20
Filing date: 1979-06-20
Publication date: 1980-01-09
Also published as: DE2924894A1; AU4820679A; ZA793077B; DD144411A5; BR7903890A; FR2429215A1; US4238388A; DK255279A; NL7904838A; ES481700A1; IT1096590B; IT7824744A0; LU81406A1; JPS557273A; CS212235B2; BE877116A

Description

1

GB 2 024 217 A

1

SPECIFICATION

1,3,5-triazacycloheptane -2,4-dione derivatives

* 5 This invention relatesto new piperidine compounds in the form of derivates of 1,3,5-triazacycloheptane-2,4-dione,the process for their preparation and their use as stabilisers against light, heat and oxidation for synthetic polymers.

More precisely, this invention relatesto new compounds of formula

10 t3 *4 % Rio p „ 10

15 nH 1 p—"R_ 15

20 .20

in which:

Ri, R12 which can be equal or different, represent-0°, -CN, hydrogen, a linear or branched alkyl containing 1 to 20 carbon atoms, an alkenyl or alkinyl containing 2 to 20 carbon atoms, benzyl, benzyl substituted by 1 to 3 alkyls containing 1 to 4 carbon atoms, hydroxybenzyl, hydroxybenzyl substituted by 1 to 3 alkyls containing 25 1 to 4 carbon atoms; a -COR15, -COORis or -CONRi5R16 radical in which Rns, R16, which can be equal or 25

different, represent a linear or branched alkyl containing 1 to 20 carbon atoms, an alkenyl containing 2 to 20 carbon atoms, a cycloalkyl containing 5 to 12 carbon atoms, an aryl containing 6 to 12 carbon atoms^an aralkyl containing 7 to 18 carbon atoms or when bonded to N they can be hydrogen, or together with the N to which they are bonded they can form a nitrogenous heterocyclic ring of 5 to 8 terms; or a 30 -CH2-CH-R14 30

radical in which R-|3 is hydrogen, methyl or phenyl and R14 is -OH, -CN, 0 -OR15, -COOR15, -COR^, 35 -OCOR15, -CONRiSR16, -OOONR15Ri6, -NR15Ri6 in which R15 and R16 are as heretofore defined: 35

R2, R3, R6, R7, which can be equal or different, represent an alkyl containing 1 to 6 carbon atoms;

R4, R5, which can be equal or different, represent hydrogen or an alkyl containing 1 to 6 carbon atoms;

Rs, Rg, R10, R11, which can be equal or different, represent hydrogen or an alkyl containing 1 to 6 carbon 40 atoms. 40

The following can be indicated as particular examples of the various radicals:

For R1f R12: hydrogen, methyl, ethyl, n-propyl, n-butyl, isobutyl, n-hexyl, n-octyl, n-decyl, n-dodecyl', n-octadecyl, allyl, 2-butenyl, 10-undecenyl, oleyl, propargyl, benzyl, 4-methy I benzyl, 4-tert-butylbenzyl, 4-hydroxybenzyl, 3,5-di-tert-butyl-4-hydroxybenzyl, and when they are represented by a 45 45

-CH2-CH-R14

Rl3

50 radical, then R13 could in particular be hydrogen, methyl or phenyl, and R14 could in particular be-OH,-CN 50

•or '

''55 Examples of R15, R16 are methyl, ethyl, n-propyl, n-butyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, allyl, 55

2-butenyl, 10-undecenyl, oleyl, cyclohexyl, 2- or4-methylcyclohexyl, 3,3,5-trimethylcyclohexyl, phenyl, 2- or 4-methylphenyl, 2,4- or 2,6-dimethylphenyl, 4-tert-butylphenyl, benzyl, 4-methylbenzyl, 4-tert-butylbenzyl, or when bonded to an N they can be hydrogen or pyrrolidinyl, piperidinyl, morpholinyl, piperazinyl, N-methylpiperazinyl, homopiperazinyl, or N-methylhomopiperazinyl.

60 Preferred examples of R2, R3, R6, R7 are methyl or ethyl, and R4, Rs are preferably hydrogen or methyl. 60

Particularly preferred combinations are:

a) R2/ R3< R6. R7 = methyl, R4, R5 = hydrogen; b) R2, R4/ R6 = methyl, R3, R7 = ethyl, R5 = hydrogen.

Rg, R9, R10, R11 are preferably hydrogen or methyl.

The new derivatives of 1,3,5-triazacycloheptane-2,4-dione as heretofore defined are prepared according to 65 the present invention by reacting a N,N'-bis(polyalkyl-4-piperidyl) ethylenediamine of formula: 65

2

GB 2 024 217 A

2

i r3 ? 4

r,— n

R8 R10

nh— c— c— nh r9 r11

10

ii in which R1f R2, R3, R4, R5, R6, R7, Rs» R9' Rio, Rn are as heretofore defined, with urea or biuret. If urea is used, the molar ratio of compounds of formula II to urea lies between 1:3 and 1:1.5, and preferably between 1:2.25 and 1:1.75. If biuret is used, the molar ratio of compounds of formula II to biuret lies between 1:1.25 and 1:0.75, and preferably between 1:1.1 and 1:0.9.

15 The reaction can be carried out either with or without solvent, at a temperature of 50° to 250°C, preferably 100 to 200°C, and at a pressure of 0.5 to 10 atmospheres. The reaction solvent used can be an organic inert solvent such as dimethylformamide, dimethylacetamide, dimethylsulphoxide, chlorobenzene, dichloroben-zene, n-butanol, n-pentanol, n-hexanol, 2-ethoxyethanol, 2-butoxyethanol, ethyleneglycol, toluene, xylene, ethylbenzene, diethyl benzene or decahydronaphthalene.

20 By reacting bispiperidylamines of formula II with urea or biuret, compounds are obtained of formula:

10

15

20

25

30

3 ir4

2

r..— n

6 r5

f9 I"

*8ry \ Rn

- n n

n '

I

h f4 ?3

2

N—R-,

r5 r6

iii

25

30

in which Rn, R2, R3, R4, R5, R6, R7, R* R9/ Rio» R11 are as heretofore defined.

The products III can be the final products according to the invention, if it is required to obtain compounds 35 where R12 = H. If it is required to obtain products I in which R12 is otherthan hydrogen, the compounds III are reacted with a compound of formula X - R12 (IV), in which R12 has any of the aforesaid meanings with the exception of hydrogen, and X is a halogen, preferably CI, Br or I.

If R1 is otherthan H in compound III, then the substitution can take place only on the imido NH of the cycloheptane ring.

If R1 = H in compound III, then different operating methods have to be used according to whether it is required to introduce equal radicals in the three available NH groups, or introduce a radical only in the irpido NH.

In the first case, fairly severe reaction conditions and very energetic reagents are used, i.e. compounds of formula IV in which X is a very reactive halogen.

For selectively substituting only the imido group in the cycloheptane ring, more gentle conditions are used, together with less reactive compounds of formula IV.

The compounds of formula II, which are the starting substances for the process according to the present invention, are prepared using the process described in USA patent 3 480 635 by the reductive alkylation of diamines

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50

R1

55

H2N-C— C— NHZ

I I

Rg R11

* 55

with polyalkyl-4-piperidones of formula

*2'

R,— N

l«A

R6 R5

3 GB 2 024 217 A

, in the presence of hydrogen, and of platinum as catalyst.

According to an alternative embodiment of the present process, when R-i = R12 = H in the compounds III, it is possible to introduce the methyl radical only in the piperidine NH's by means of the Eschweiler-Clarke % reaction (Organic Reactions Vol. V- page 307, Wiley & Sons 1962).

5 Preferred examples of compounds according to the present invention are:

- 1,5-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,3,5-triazacycloheptane-2,4-dione

- 1,5-bis(2,2,6,6-tetramethyl-4-piperidyl)-6-methyl-1,3,5-triazacyclo-heptane-2,4-dione -1,5-bis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,3,5-triazacycloheptane-2,4-dione -1,5-bis(1,2,2,6,6-pentamethyl-4-piperidyl)6-methyl-1,3,5-triazacyclo-heptane-2,4-dione

10 - 1,5-bis(1-ethyl-2,2,6,6-tetramethyl-4-piperidy[)-1,3,5-triazacycloheptane-2,4-dione

- 1,5-bis(2,6-diethyl-2,3,6-trimethyl-4piperidyl)-1,3,5-triazacycloheptane-2,4-dione

- 1,5-bis(2,6-diethyl-1,2,3,6-tetramethyi-4-piperidyl)-1,3,5-triazacycloheptane-2,4-dione

- 1,5-bis(1-n-propyl-2,2,6,6-tetramethyl-4-piperidyl)-1,3,5-triazacycloheptane-2,4-dione

- 1,5-bis(1-n-butyl-2,2,6,6-tetramethyl-4-piperidyl)-1,3,5-triazacyclo-heptane-2,4-dione

15 - 1,5-bis(1-n-butyl-2,2,6,6-tetramethyl-4-piperidyl)-6-methyl-1,3,5-triazacycloheptane-2,4-dione

- 1,5-bis(1-a7-hexyl-2,2,6,6-tetramethyl-4-piperidyi)-1,3,5-triazacyclo-heptane-2,4-dione

- 1,5-bis(1-n-octyl-2,2,6,6-tetramethyl-4-piperidyl)-1,3,5-triazacyclo-heptane-2,4-dione

- 1,5-bis(1-benzyl-2,2,6,6-tetramethyl-4-piperidyl)-1,3,5-triazacyclo-heptane-2,4-dione

- 1,5-bis(1-ethoxycarbonylmethyl-2,2,6,6-tetramethyl-4-piperidyl)-1,3,5-triazacycloheptane-2,4-dione 20 - 1,5-bis(1(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidyl)-1,3,5-triazacycloheptane-2,4-dione

- 1,5-bis(1(2-cyanoethyl)-2,2,6,6-tetramethyl-4-piperidyl)-1,3,5-triazacycloheptane-2,4-dione

- 1,5-bis(1-acetyl-2,2,6,6-tetramethyl-4-piperidyl)-1,3,5-triazacyclo-heptane-2,4-dione

- 1,5-bis(1-acetyl-2,2,6,6-tetramethyl-4-piperidyl)-6-methyl,1,3,5-triazacycloheptane-2,4-dione . - 1,5-bis(2,2,6,6-tetramethyl-4-piperidyl)-3-methyl-1,3,5-triazacyclo-heptane-2,4-dione

2>5 - 1,5-bis(2,2,6,6-tetramethyl-4-piperidyl)-3-ethyl-1,3,5-triazacyclo-heptane-2,4-dione

- 1,5-bis(2,2,6,6-tetramethyl-4-piperidyl)-3-n-butyl-1,3,5-triazacyclo-heptane-2,4-dione

- 1,5-bis(1,2,2,6,6-pentamethyl-4-piperidyl)-3-methyl-1,3,5-triazacyclo-heptane-2,4-dione

- 1,5-bis(1,2,2,6,6-pentamethyl-4-piperidyl)-3,6-dimethyl-1,3,5-triazacyclopheptane-2,4-dione

- 1,5-bis(1,2,2,6,6-pentamethyl-4-piperidyl)-3-n-butyl-1,3,5-triazacyclo-heptane-2,4-dione

30 - 1,5-bis(1-n-butyl-2,2,6,6-tetramethyl-4-piperidyl)-3-n-butyl-1,3,5-triazacycloheptane-2,4-dione

A detailed description is given hereinafter of the process for preparing some of the aforesaid compounds, by way of non-limiting example only.

EXAMPLE 1

35 338 g (1 mole) of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl) ethylenediamine, 120 g (2 moles) of urea and 500 ml of dimethylformamide are heated under a slight nitrogen current for two hours at 130°C and then for 16 hours at 140-145°C.

On cooling to ambient temperature, a crystalline precipitate is obtained which is separated by filtration, washed with a little acetone, dried and recrystallised from ethanol. A compound is obtained of formula:

50

M.P. 270-274°C « Analysis for C22H41N5O2

calculated: C 64.83%; H 10.14%; N 17.18%

55

found : C64.61%; H 10.21%; N 17.06%

1,5-bis(2,2,6,6-tetramethyl-4-piperidyl)-6-methyl-1,3,5-triazacyclopheptane-2,4-dione having an M.P. of 305-308°C was prepared in the same manner.

60

EXAMPLE 2

The product described in Example 1 is prepared by heating 338 g (1 mole) of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl) ethylenediamine, 103 g (1 mole) of biuret and 500 ml of dimethylformamide for 10 hours at 140-145°C.

gg After crystallising from ethanol, the product obtained has an M.P. of 271-274°C.

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4

GB 2 024 217 A

4

EXAMPLE 3

40.7 g(0.1 moles) of 1,5-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,3,5-triazacycloheptane-2,4-dione prepared as t in Example 1,50 ml of 85% formic acid and 100 ml of 37% formaldehyde are heated under reflux for 8 hours.

After cooling to ambient temperature, the reaction mixture is diluted with 200 cc of water and aikalised 5 with 10% aqueous NaOH. 5*

The precipitate obtained is separated by filtration, washed with water, dried and crystallised from methanol.

A compound is obtained of formula:

10 ph„ 10

r,c h3c_ n r\.

*

3 -ch

3

n ch„

15 Hqc ] N _£_ch 15

-f h,c i

20 20

M.P. 248-251 °C Analysis for C24H45N502

C

calculated: C 66.17%; H 10.41%; N 16.07%

25 25

found : C 65.92%; H 10.32%; N 15.95%

EXAMPLE4

40.7 g (0.1 moles) of 1,5-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,3,5-triazacyclopheptane-2,4-dione, 70.95 g 30 (0.5 moles) of methyl iodide, 250 ml of xylene, 40 g of 50% aqueous sodium hydrate and 3.5 g of 30

lauryl-dimethylbenzylammonium chloride are heated under reflux for 5 hours. 20 ml of water are added to the reaction mixture, the aqueous layer is separated, it is made completely anhydrous by azeotrope formation, is filtered hot and is cooled.

The crystalline precipitate obtained is separated by filtration and recrystallised from acetone. 35 A compound is obtained of formula: 35

h„c

"3/ \ / \ /~V"3

40 H3°—N. ) n n ( \ —pit 40

J t rs—n M

t7 ..L.X ^

3 \ n ^ h„c

3

45 45

3

M.P. 201-203°C Analysis for C25H47N5O2

50 50

calculated: C 66.77%; H 10.53%; N 15.57%

found : C 66.41%; H 10.68%;

N 15.45%

5

GB 2 024 217 A

5

EXAMPLE 5

40.7 g (0.1 moles) of 1,5-bis(2,2,6,6-tetramethyl-4piperidyl)-1,3,5-triazacycloheptane-2,4-dione, 20.55 g (0.15 moles) of n-butylbromide; 250 ml of xylene, 40 g of 50% aqueous sodium hydrate and 3.5 g of lauryl-dimetylbenzylammonium chloride are heated under reflux for 6 hours. 20 ml of water are added to the reaction mixture, the aqueous layer is separated and the organic phase is evaporated to dryness.

The waxy residue obtained is crystallised from n-hexane. A compound is obtained of formula:

10

15

?3c

"YCH3

nh

J-

h3g

10

15

'4 9

M.P. 151-2°C 20 Analysis for C26H49N5O2

20

calculated:

C 67.34%;

H 10.65%;

N 15.10%

found

C 67.05%;

H 10.52%;

25

N 14.93%

EXAMPLE 6

46.3 g (0.1 moles) of 1,5-bis(2,2,6,6-tetramethyl-4-piperidyl)-3-n-bu-ty!-1,3,5-triazacycloheptane-2,4-dione prepared as in Example 5,42.6 g (0.3 moles) of methyl iodide, 27.6 g (0.2 moles) or anhydrouspotassium carbonate and 200 ml of xylene are heated under reflux for 4 hours. The inorganic products are separated by 30 filtration, and the filtrate is evaporated to dryness.

The residue obtained is crystallised from octane.

A compound is obtained of formula:

25

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35

40

45

h3c-n

M.P. 172-4°C Analysis for C28H53NS02

35

40

45

calculated:

50

found

C 68.39%; C 68.18%;

H 10.86%; H 10.71%;

N 14.24% N 14.17%

As stated at the beginning of this patent application, compounds of formula I are very effective in increasing the light, heat and oxidation resistance of synthetic polymers such as high and low density 55 polyethylene, polypropilene, ethyiene-propylene copolymers, ethylene-vinylacetate, copolymers, polybuta-diene, polyisoprene, polystyrene, butadiene-styrene copolymers, acrylonitrile-butadiene-styrene copolymers, polymers and copolymers of vinyl chloride and vinylidene chloride, polyoxymethylene, polyurethane, unsaturated polyesters, polyamides, polycarbonates, polyacrylates, alkyd resins and epoxy resins.

The compounds of formula I can be used in mixture with synthetic polymers in various proportions 60 depending on the nature of the polymer, the final application and the presence of other additives.

In general, it is suitable to use 0.01 to 5% by weight of the compounds of formula I with respect to the weight of the polymers, and preferably 0.1 to 1%.

The compounds of formula I can be incorporated into the polymer materials by various methods such as dry mixing in the form of a powder, or wet mixing in the form of a solution or suspension, or in the form of a 65 master batch. In these operations, the synthetic polymer can be used in the form of a powder, granulate,

50

55

60

65

6

GB 2 024 217 A

6

solution, suspension or emulsion. The polymers stabilised with the products of formula I can be used for preparing moulded objects, film, narrow strips, fibres, monofilaments, lacquers and the like.

The mixtures of compounds of formula I with synthetic polymers are compatible with other additives for polymers such as antioxidants, UV absorbers, nickel stabilisers, pigments, fillers, plasticisers, antistatic 5 agents, antifire agents, lubricants, anticorrosive agents and metal deactivators.

Examples of additives which can be used in mixture with the compounds of formula I are, in particular:

phenolic antioxidants, such as 2,6-di-tert-butyl-p- cresol, 4,4'-thiobis-(3-methyl-6-tert-butylphenol), 1,1,3-tris-(2-methyl-4-hydroxy-5-tert-butylphenyl)-butane, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate, pentaerythritol-tetra-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate, tris-(3,5-di-tert-butyl-4-10 hydroxybenzyD-isocyanurate, tris-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-isocyanurate;

secondary antioxidants such as esters of thiodipropionic acid, such as di-n-dodecyl-thiodipropionate, di-n-octadecyl-thiodipropionate;

secondary antioxidants such as aliphatic sulphides and disulphides, such as di-n-dodecyl-sulphide, di-n-octadecyl-sulphide, di-n-octadecyl-disulphide;

15 secondary antioxidants such as aliphatic, aromatic or aliphatic-aromatic phosphites and thiophosphites, such as tri-n-dodecylphosphite, tris-nonylphenyl-phosphite, tri-n-dodecyl-trithiophosphite, phenyl-di-n-decylphosphite, di-n-octadecyl-pentaerythritol-diphosphite, tris-(2,4-di-t-butylphenyl)-phosphite, tetrakis-(2,4-di-tert-butylphenyl)-4,4'-diphenylene-diphosphonite;

UV absorbers such as 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecoxybenzophenone, 2-(2'-20 hydroxy-3',5'-di-tert-butyphenyl)-5-chloro-benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-amylphenyl)-

benzotriazole, 2,4-di-tert-butylphenyi-3,5-di-tert-butyl-4-hydroxybenzoate, phenylsalicylate,p-t-butylphenyl-salicylate, 2,2'-di-n-octoxy-5,5'-di-tert-butyloxanilide, 2-ethoxy-5-tert-butyl-2'-ethoxyanilide, ethyl-a-cyan-B,B-diphenylacrylate, methyl-a-cyan-[3-methyl-4-methoxycinnamate;

nickel-based light stabilisers such as Ni-monoethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphate, butylamine-25 Ni-2,2'-thiobis-(4-t-octylphenolate) complex, Ni-2,2'-thiobis-4-tert-octylphenolphenolate), Ni-dibutyldithio-carbamate, Ni-3,5-di-tert-butyl-4-hydroxybenzoate, Ni complex of 2-hydroxy-4-n-octoxybenzophenone; organostannic stabilisers such as dibutyltin-maleate, dibutyltinlaurate, dioctyltin-maleate;

metal salts of higher fatty acids such as calcium, barium, cadmium, zinc, lead, nickel stearates;

calcium, cadmium, zinc, barium laurates;

30 organic and inorganic pigments such as Color Index Pigment Yellow 37, Color Index Pigment Yellow 83, Color Index Pigment Red 144, Color Index Pigment Red 48:3, Color Index Pigment Blue 15, Color Index Pigment Green 7, titanium dioxide, iron oxide and the like.

The effectivness of the products prepared according to the invention as stabilisers is illustrated in the following examples in which some of the products obtained in the examples of preparation are used in a 35 synthetic polymer composition and subjected to stability tests.

The results are given in comparison with those obtained adding known stabilisers available commercially.

EXAMPLE 7

2 g of each of the compounds indicated in Table 1 and 1 g of 2,6-di-tertbutyl-p-cresol (as antioxidant)dis-40 solved in 100 ml of methanol are mixed with 1000 g of polypropylene MI=3.2(Moplen C (Registered Trade Mark), produced by Montedison) and 1 g of calcium stearate.

The solvent is removed in an oven under vacuum at a temperature of 50°Cfor4hours.

The dry mixture obtained is then extruded at a temperature of 200-230°C and transformed into granules, from which plates are obtained having a thickness of 0.2 mm by die-casting to 200°C. The plates are exposed 45 in a 65 WR Weather-Ometer(ASTM G 27-70) with a black panel temperature of 63°C, and the increase in the content of carbonyl groups (A CO) is checked periodically using the non-exposed samples for compensating the initial absorption of the polymer. The time (T 0.1) necessary forgiving a ACO% = 0.1 at 5.85 jim is calculated.

As a comparison, a polymer plate without adding the stabilisers of the present invention is prepared, as is 50 a plate adding 2 g of 2-hydroxy-4-n-octoxybenzophenone as light stabilisers, these plates being prepared under the same conditions.

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X

8

GB 2 024 217 A

8

a) without adding a light stabilisers b) with the addition of 2 g 2-hydroxy-4-n-octoxybenzophenone as a light stabiliser in place of the new stabilisers

TABLE 3

10

Stabiliser

Without light stabiliser 2-hydroxy-4-n-octoxybenzphenone Compound of example 1 15 Compound of example 3 Compound of example 4 Compound of example 5

20

Compound of example 6

T 0.1 (hours)

320 1000 >4000 >4000 >4000 >4000 >4000

10

15

20

EXAMPLE 10

2 g of each of the compounds listed in Table 4 are mixed with 1000 g of low density polyethylene of

25 Ml=0.26 (Fertene ZF 5-1800, produced by Montedison), 0.5 g of 2,6-di-tert-butyl-p-cresol (as antioxidant), 25 and 1 g of calcium stearate in a low speed mixer.

The mixture obtained is then extruded at 190°C and transformed into granules, from which plates having a thickness of 0.2 mm are obtained by diecasting at 200°C, these then being exposed in a Xenotest 150 (Registered Trade Mark) (temperature of black panel 60°C- DIN 54004).

30 The time (T 0.5) necessary for giving an increase in the content of carbonyl groups, A CO%, of 0.5 at 30

5.85 (xm is then determined.

As a comparison, polymer plates are prepared under the same conditions as follows:

a) without adding light stabilisers b) with the addition of 2 g of 2-hydroxy-4-n-octoxybenzophenone as a light stabiliser.

35 Table 4 gives the results obtained. 35

TABLE 4

Stabiliser

Without light stabiliser 2-hydroxy-4-n-octoxybenzophenone Compound of example 1 Compound of example 3 Compound of example 4 Compound of example 5 Compound of example 6

T 0.5 (hours) 860 1600 >4000 >4000 >4000 >4000 >4000

7

GB 2 024 217 A 7

Table 1 gives the results obtained.

TABLE 1

' 5 Stabiliser

TO. 1 (hours)

Without light stabiliser

210

2-hydroxy-4-n-octoxybenzophenone

650

10

Compound of example 1

1580

Compound of example 3

1950

15 Compound of example 4

2320

Compound of example 5

1830

„ Compound of example 6

1970

20

EXAMPLE 8

The polypropylene granules prepared as described in example 7 are transformed by extrusion into strips having a thickness of 40 ^m and a width of 3 mm.

The operating conditions are:

25

temperature of extruder : 230-240°C

temperature of head : 240°C

30 stretching ratio : 1:6

The strips obtained are exposed in a 65 WR Weather-Ometer under the conditions indicated in example 7. Samples are withdrawn periodically, of which the residual toughness is measured by means of a constant speed dynamometer. The exposure time necessary for halving the initial toughness (T50) is then evaluated.

35

Table 2 shows the results obtained.

- TABLE 2

40 Stabiliser T50 (hours)

2-hydroxy-4-n-octoxybenzophenone 300

Compound of example 1 1020

45

Compound of example 3 1370

Compound of example 4 1530

50 Compound of example 5 1290

* Compound of example 6 1450 EXAMPLE 9

55 2g of each of the compounds given in Table 3 dissolved in 100 ml of methanol are mixed with 1000 g of high density polyethylene of Ml=0.32 (Moplen RO, produced by Montedison), 0.5 g of tris(3,5-di-tert-butyl-4-hydroxy-benzyl)isocyanurate as antioxidant, and 1 g of calcium stearate.

The solvent is removed in an oven under vacuum at a temperature of 50°Cforfour hours.

The dry mixture obtained is then extruded at a temperature of 190°C and transformed into granules, from 60 which plates of 0.2 mm thickness are obtained by die-casting at 200°C.

The plates are exposed in a 65 WR Weather-Ometer with a black panel temperature of 63°C, and the increases in the content of carbonyl groups (A CO) is checked periodically, using the non-exposed samples for compensating the initial absorption of the polymer. The time (T 0.1) necessary for giving a A C0%=0.1 at 5.85 ixm is calculated.

65 As a comparison, polymer plates are prepared under the same conditions as follows:

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GB 2 024 217 A

9

Claims

CLAIMS 1. Compounds of formula

5

10

15

?9 ?10 *8 J Rn —'N N

12

^4 h

N R,

R* R«

5 6

10

15

in which:

R1f R12, which can be equal or different, represent -0°, -CN, a linear or branched alkyl containing 1 to 20 . carbon atoms, an alkenyl containing 2 to 20 carbon atoms, benzyl, benzyl substituted by 1 to 3 alkyls 20 containing 1 to 4 carbon atoms, hydroxybenzyl, hydroxybenzyl substituted by 1 to 3 alkyls containing 1 to 4 20 carbon atoms; a -CORi5'-COORi5 or-CONRi5R16 radical in which R-|S, R-|6, which'can be equal or different, represent a linear or branched alkyl containing 1 to 20 carbon atoms, an alkenyl containing 2 to 20 carbon atoms, a cycloalkyl containing 5 to 12 carbon atoms, an aryl containing 6 to 12 carbon atoms, an aralkyl containing 7 to 12 carbon atoms or when bonded to N they Gan be hydrogen, or together with the N to which 25 they are bonded can form a nitrogenous heterocyclic ring of 5 to 8 terms; or a 25

-CH2-CH-R14

>13

30

—CH

CH,

radical in which R-i3 is hydrogen, methyl or phenyl, and R14 is OH, -CN, ^0 -OR-|5, -COOR15, -COR15,

-OCOR15, -CONRnsR16, -OCONR15R16, -NR15R16 in which R-,s and Rn6 are as heretofore defined;

R2, R3- R6/ R7, which can be equal or different, represent an alkyl containing 1 to 6 carbon atoms;

R4, Rs, which can be equal or different, represent hydrogen or an alkyl containing 1 to 6 carbon atoms; 35 R8, Rg, Rior R11, which can be equal or different, represent hydrogen or an alkyl containing 1 to 6 carbon atoms.

2. Compounds as claimed in claim 1 in which R1f R-|2, which can be equal or different, are hydrogen or a linear or branched CrC6 alkyl; R2, R3, R6, R?< which can be equal or different, are methyl or ethyl; R4, R5, which can be equal or different, are hydrogen or methyl; and R8, R9, R10, Rn, which can be equal or different,

40 are hydrogen or methyl.

3. Acompound as claimed in claim 1 of formula

CH,

h3c

45

50

NH

H3^f

CH_

■ CHr

NH JCH,

h3c

30

35

40

45

50

4. A compound as claimed in claim 1 of formula -H„

10

GB 2 024 217 A

10

5. A compound as claimed in claim 1 of formula

CH„

20

I

25

7. A compound as claimed in claim 1 of formula

4H9

40 8. A compound as claimed in claim 1 of formula

50

9. A process for preparing compounds of formula r12

h„c ch

I I3

3/ \ / \

3C_N \ N N -/ )

. J r

CH3 0=KkS=0 Jr

3

f CHg 'CH,

3""'

3

*3 H„C

10 cS,

6. A compound as claimed in claim 1 of formula

15

"*CJ\ / \ /~\

NH } N N ( Nl

— A L —f

CH3 H>

CHg

9*3 H3(

„?r~\ ^ /~vCHs

3 r N N- ( N—CH

•'V7 J. L. W

^H3 9H3 H,3C

X.X. H

i

3 ^N' H3C

f3 ?4 ?9 SlO R- R„

la |iu |4 ?3

"8 / \ Bn / V*2

Rj— N \ N N ( N R

-W j, iTVf -

6 5 N R5 R6

10

#

15 20 25

30

3

CH

35 CH3 U=^n^=° H3C 3 35

I

C4H9

40

45 HN ) N N ( NH 45

50

11

GB 2 024 217 A

11

in which

" R1f R12, which can be equal or different, represent-O; -CN, hydrogen, a linear or branched alkyl containing 1 to 20 carbon atoms, an alkenyl or alkinyl containing 2 to 20 carbon atoms, benzyl, benzyl substituted by 1 to 3 alkyls containing 1 to 4 carbon atoms, hydroxybenzyl, hydroxybenzyl substituted by 1 to 3 alkyls containing 1

1 5 to 4 carbon atoms; a-COR15,-COORi5 or-CONRi5R16 radical in which R15,Ri6, which can be equal or 5

different, represent a linear or branched alkyl containing 1 to 20 carbon atoms, an alkenyl containing 2 to 20 carbon atoms, a cycloalkyl containing 5 to 12 carbon atoms, an aryl containing 6 to 12 carbon atoms an aralkyl containing 7 to 12 carbon atoms or when bonded to N they can be hydrogen, or together with the N to which they are bonded they can form a nitrogenous heterocyclic ring of 5 to 8 terms; or a -CH2-CH-R14

10 I 10

. . Rl3

radical in which R13 is hydrogen, methyl or phenyl, and R14 is-OH,-CN, 0 -OR-is,-COOR15,-COR15,

15 -OCOR15, -CONR1sR16, -OCONR15R16, -NR15R16 in which R1S and R16 are as heretofore defined; 15

R2, R3, Re, R7, which can be equal or different, repesent an alkyl containing 1 to 6 carbon atoms;

r4, r5, which can be equal or different, represent hydrogen or an alkyl containing 1 to 6 carbon atoms; and Rs, Rg, R10, R11f which can be equal or different, represent hydrogen or an alkyl containing 1 to 6 carbon atoms, wherein a N,N'-bis(polyalkyl-4-piperidyl)ethylenediamine of formula

20

25

30

|r3 r4

fs fio

71

Rn— N > NH— c—C—NH

r9 r11

6 "5

20

25

II 30

35

in which R1( R2, R3, R4, R5, R6, R7, R8, R9, R10, Rn are as heretofore defined, is reacted with urea or biuret at a temperature of 50° to 250°C and at a pressure of 0.5 to 10 atmospheres, and the compound of formula I obtained in which R12 = H is possibly reacted with a compound of formula X-R12 in which X = CI, Br, I, and 35 R12 has all the meanings as heretofore defined, with the exception of hydrogen.

10. A process as claimed in claim 9, wherein the reaction is carried out with urea, the molar ratio of the compound of formula II to urea lies between 1:3 and 1:1.5, and preferably between 1:2.25 and 1:1.75.

11. A process as claimed in claim 9, characterised in that when the reaction is carried out with biuret, the molar ratio of the compound of formula II to biuret lies between 1:1.25 and 1:0.75, and preferably between

40 1:1.1 and 1:0.9. 40

12. A process as claimed in claim 9, wherein compounds of formula I in which Rt = methyl are prepared by reacting compounds of formula I in which R^i = H, with formic acid and formaldehyde.

13. A process as claimed in claim 9, wherein compounds of formula I in which Rt = R12 are prepared by reacting a compound of formula II in which R-i = H with urea or biuret, and reacting the product obtained

45 with a compound of formula X-R12 in which X is iodine.

14. A process as claimed in claim 9, wherein compounds of formula I in which R1 = H and R12 = H are prepared by reacting a compound of formula I in which RT = R1Z = H, with a compound of formula X - R12 in which X is chlorine or bromine.

15. Polymer compositions stabilised against light, heat and oxidation, comprising a synthetic polymer 50 and a stabilising compound of formula I as claimed in claim 1, in a quantity of 0.01 to 5%, and preferably 0.1

to 1%, by weight with respect to the weight of the synthetic polymer.

16. Polymer compositions as claimed in claim 15, which in addition to the stabilisers also comprise other normal additives for synthetic polymers.

17. Polymer compositions as claimed in claim 15, wherein the synthetic polymer is high density or low 55 density polyethylene.

18. Polymer compositions as claimed in claim 15, wherein the synthetic polymer is polypropylene.

19. Manufactured articles obtained from stabilised polymer composition as claimed in claims 15 to 18.

20. Compounds according to claim 1 of the formula (I), wherein R2 and R6 are methyl, R4 is hydrogen or methyl, R5 denotes hydrogen and R3 and R7 represent a group -CH2-R4 wherein R4 is as defined above.

60 21. Compounds according to claim 20 of the formula (I), wherein R2, R3, R6, R7 are methyl and R4is hydrogen.

22. A process according to claim 9 as herein described in any of the Examples.

55

60

Printed for Her Majesty's Stationery Office, by Croydon Printing Company Limited, Croydon Surrey, 1980. Published by the Patent Office, 25 Southampton Buildings, London, WC2A 1 AY, from which copies may be obtained.